Experimentally observed all-boron fullerene, B-80, inspires systematic investigation of its physical chemical properties and search for possible applications. We hereby report density functional theory calculations to characterize interactions of B-80 with the selected imidazolium room-temperature ionic liquids (RTILs), dimethylimidazolium nitrate and dimethylimidazolium hexafluorophosphate. Whereas the imidazolium cation exhibits a rather poor affinity to B-80, the inorganic anions form polar covalent bonds with the boron atom occupying a central position within a B-6 hexagon. Attachment of the RTIL ion pairs leads to a significant alteration of the electronic spectra, charge density distribution, valence and conduction molecular orbitals. The total binding energies keeping the RTIL@B-80 complexes together range 200250 kcal mol(-1), being higher than the energies of many interactions in chemistry. The observed phenomenon predicts an excellent solubility of B-80 in the considered RTILs, but may also reveal a poor stability of B-80 in the polar media. Our results motivate further efforts in studying the behavior of the all boron fullerene in polar environments. (C) 2017 Elsevier B.V. All rights reserved.